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Chapter 1 Introduction...........................................................................................1
References.............................................................................................4
vii
viii Contents
Summary................................................................................................................205
List of Abbreviations.............................................................................................207
Index.......................................................................................................................211
Preface
Adsorption and desorption in solution play significant roles in separation, detoxi-
fication of waste streams, purification, chromatography, heterogeneous catalysis,
metabolism of medicinal drugs, and more. Metal–organic frameworks (MOFs)
are well-ordered 3D hybrid organic–inorganic polymers that contain metal cations
and structure-building organic “linker” units. Mesoporous MOFs with pore sizes
2–50 nm are particularly suitable for adsorption and adsorption-based separations of
large molecules of organic and bio-organic compounds.
Thousands of organic compounds and in particular aromatic and heterocyclic
compounds are widely used as feedstock for industrial chemical synthesis and as fine
chemicals, major components of liquid fossil fuels, dyestuffs, industrial solvents,
agricultural chemicals, medicinal drugs, pharmaceuticals and personal care products
(PPCPs), active pharmaceutical ingredients (APIs), and so on.
There is strong interest in the synthesis, characterization, and studies of both
known and newly synthesized mesoporous MOFs for adsorption in solution to
achieve high adsorption capacity, selectivity, and the possibility of multiple regen-
eration of the “spent” sorbent.
This book is intended to cover experimental fundamental research on using mes-
oporous MOFs for emerging applications of major industrial, environmental, and
academic importance, especially for purification and separations of water and liquid
fossil fuels.
xi
List of Figures
Figure 1.1 S
chematic presentation for the construction of typical
coordination polymers/MOFs from molecular building blocks..........2
Figure 1.2 T
he number of research papers published annually
on mesoporous MOFs..........................................................................2
Figure 2.1 Basic building units and crystal structure of MIL-101........................6
Figure 2.2 S
chematic representation of the synthesis of Pt nanoparticles
inside the MIL-101 matrix using the “double solvents” method.........8
Figure 2.3 S
chematic representation of the post-synthetic modification
of Cr-MIL-101.....................................................................................9
Figure 2.4 1 H NMR spectrum of the linker of Cr-MIL-101–UR2
measured in NaOD/D2O (20%)...........................................................9
Figure 2.5 P
ost-synthetic modification of Cr-MIL-101-NH2 with
p-phenylazobenzoylchloride (1) and 4-(phenylazo)
phenylisocyanate (2)..........................................................................10
Figure 2.6 R
eaction of 2-aminoterephthalic acid (2-ATA) and
4-methylaminopyridine (4-MAP) conjugation using DSS as an
activating agent..................................................................................11
Figure 2.7 P
ost-synthetic modification of Al-MIL-101-NH2 by treatment
with phenylisocyanate.......................................................................11
Figure 2.8 Parameters investigated for the optimization of the two-step
peptide grafting process into various MOFs......................................12
Figure 2.9 Tandem post-synthetic modification of MIL-101(Cr)-NH2...............13
Figure 2.10 Structure of MIL-100(Fe)..................................................................14
Figure 2.11 Synthesis of [SO3H–(CH2)3–HIM]3PW12O40@MIL-100...................17
Figure 2.12 S
chematic illustration of the formation of heparin-coated
MIL-100(Fe) NPs loaded with specific cargoes via two
differentiated pathways......................................................................17
xiii
xiv List of Figures
Figure 4.1 Schematic representation of (a) the unit cell of MIL-101 crystal
structure with the boundaries of two types of cages (large cage
shown in pink, and small cage shown as a blue circle); (b)
polyhedral model view of the two cages; (c) the trimeric building
block sharing an oxygen center and chelated by six carboxylates.
Chromium octahedra, oxygen, and carbon atoms are in green, red,
and blue, respectively. (d) Evolution of unsaturated metal sites of
MIL-101 after vacuum heating, and postmodification of dehydrated
MIL-101 through coordination of DAAP-type molecules onto
its chromium unsaturated sites. The unit structure depicted
corresponds to the published structure of chromium terephthalate
MIL-101 [32] with formula Cr3OH(H2O)2O[(O2C−C6H4−(CO2)]3,
wherein fluoride is substituted with −OH, as we utilized HF-free
synthesis of the MOF [29]. The presence of three ligands (L) per
unit is shown, which corresponds to the structures of MIL-101-A,
MIL-101-B, and MIL-101-C (Table 4.1), based on elemental
analyses. Crystal structures depicted were built utilizing published
lattice parameters [29,32] and applying Crystal Maker software.............42
Figure 4.2 Catalytic hydrolysis of paraoxon with new MOF composites.............43
Figure 4.3 S
chematic 3D representation of the tetrahedra built
up from trimers of ferrum octahedra and 2-amino-1,4-
benzenedicarboxylate moieties in Fe-MIL-101–NH2..........................45
Figure 4.4 S
chematic illustration of the possible pathway of proton transfer
in the membranes. S, O, C, and N are represented as yellow, red,
gray, and blue, respectively; H atoms are omitted...............................45
Figure 4.5 T
he sequence of events during the crystallization of terephthalate-
based MOFs in different media: low precursor concentrations
(DMF) and high precursor concentrations (H2O/DMF or H2O). C,
gray; H, white; N, blue; O, red; Al, yellow; Cl, green............................46
Figure 4.6 X
RD patterns of the samples obtained at different pH with
CTAB/Al and H2O/EtOH molar ratios of 0.6 and 3.4, respectively......51
Figure 4.7 B
JH pore size distribution curves of the samples synthesized at
pH 2.5 in mixtures of H2O and EtOH with different molar ratios
and a CTAB/Al ratio of 0.6..................................................................52
Figure 4.8 S
chematic representation of the synthesis and formation of
SURMOF-2 analogues........................................................................55
Figure 4.9 O
ut of plane XRD data of Cu-BDC, Cu-2,6-NDC, Cu-BPDC,
Cu-TPDC, Cu-QPDC, Cu-P(EP)2DC and Cu-PPDC (upper
left), schematic representation (upper right) and proposed
structures of SURMOF-2 analogues (lower panel). All the
SURMOF-2 are grown on –COOH terminated SAM surface
using the LPE method..........................................................................56
xvi List of Figures
Figure 4.10 S
tructure of UMCM-1: (a) A Zn4O cluster coordinated to
two BDC linkers and four BTB linkers. Zn4O clusters, blue
tetrahedra; C, gray; H, white; O, red. (b) A microporous cage
constructed of six BDC linkers, five BTB linkers, and nine
Zn4O clusters. (c) Structure of UMCM-1 viewed along the
C-axis illustrating the one-dimensional mesopore............................57
Figure 4.11 C
rystal structure of 437-MOF. (a) Top and schematic views of
the concave triangular-prism supermolecular building block
(SBB). (b) Side and schematic views of the concave triangular-
prism SBB. (c) View of the 3D framework and the space-filling
model showing regular 1D hexagonal channels................................59
Figure 4.12 ( a) Structure of hmtt, (b) SBU of POST-66, (c) crystal structure
of POST-66, (d) octahedral cage, and (e) cuboctahedral cage...........60
Figure 4.13 ( a) Six-connected D3d-symmetric Zr6 antiprismatic units and
trigonal–planar organic linker TATB. (b) The structure of PCN-
777 with the large mesoporous cage (given in red)...........................62
Figure 4.14 S
tructure illustrations of PCN-332 and PCN-333. (a) Ligands
used in PCN-332 and PCN-333. (b) Three different cages in
PCN-332 and PCN-333. (c) Simplification of PCN-332 and
PCN-333 into MTN topology............................................................63
Figure 5.1 (a) N2 adsorption–desorption isotherms at 77 K for the
hierarchically mesostructured MIL-101 MOFs C2 (circles), B2
(upward triangles), B1 (squares), and C1 (downward triangles);
the isotherms for C2 (circles), B2 (upward triangles), and
B1 (squares) are vertically offset by 150, 200, and 50 cm3/g,
respectively. (b) Distribution of pore diameters obtained using
the DFT method; the distributions for C2, B1, and B2 are
vertically offset by 1.5, 1.0, and 0.5 cm3/g, respectively...................70
Figure 5.2 ( a) Methylene blue (MB) and (b) Rhodamine B (RhB) dyes............70
Figure 5.3 ( a) Octahedral cluster of three AlO5(OH) units with the
organic ligand aminoterephthalate. These clusters and ligands
form the framework of amino-MIL-101(Al), and each cluster
is shown in the bottom diagram as a green octahedron. (b)
Supertetrahedral building units of amino-MIL-101(Al)
formed by aminoterephthalate ligands and trimeric AlO5(OH)
octahedral clusters. Green, trimeric cluster; red, O; black, C;
blue, N; yellow, H. Only the N-bound H atoms are shown...............71
Figure 5.4 Malachite green (MG) dye................................................................73
Figure 5.5 Effect of pH on the adsorption of MG (100 mg/L) on MIL-
100(Fe) (10.0 mg) containing 0.01M NaCl, and the zeta
potential of MIL-100(Fe) (0.4 mg/L) at 30°C...................................73
List of Figures xvii
Figure 8.1 T
he palladium-catalyzed carbon–carbon functionalization of
Cr-MIL-101.....................................................................................114
Figure 8.2 ( a) The tandem postsynthetic modification (PSM) of
Cr-MIL-101–A4 to Cr-MIL-101–AS and its application
in mercury adsorption. (b) The high mercury adsorption
efficiency of Cr-MIL-101–AS in water. (c) Powder x-ray
diffraction (PXRD) measurements of Cr-MIL-101–A4,
Cr-MIL-101–AS, and Hg-adsorbed Cr-MIL-101–AS–Hg..............115
Figure 8.3 S
electivity of MIL-101, ED–MIL-101 (2 mmol), and ED–
MIL-101 (5 mmol)...........................................................................120
Figure 8.4 ( a) Generation of coordinatively unsaturated sites from
chromium trimers in MIL-101 after vacuum treatment at 423
K for 12 h; (b) adsorption principle of amino-functionalized
MIL-101 for Pb(II) ions...................................................................121
Figure 8.5 ( a) A schematic diagram of Fe3O4 functionalization by En.
(b) The schematic illustration of synthesized magnetic MOF
nanocomposite.................................................................................122
Figure 9.1 T
he representative nonbasic aromatic N-heterocyclic
compounds: (a) indole, (b) 1-methylindole, (c) 4-methylindole,
(d) carbazole, and (e) 9-methylcarbazole........................................126
Figure 9.2 T
he representative basic aromatic N-heterocyclic
compounds: (a) quinoline, (b) 8-methylquinoline, (c)
1,2,3,4-tetrahydroquinoline, and (d) isoquinoline...........................126
Figure 9.3 ( a) Effect of solvents applied in the regeneration of the used
0.25% GO/MIL-101 on the adsorptive removal of BT, QUI,
and IND. (b) Effect of regeneration cycles on the performances
of adsorptive removal of BT, QUI, and IND over regenerated
0.25% GO/MIL-101 by washing with ethanol (run 1 represents
the fresh adsorbent). The hydrocarbon solutions containing 600
ppm BT, 300 ppm QUI, and 300 ppm IND.....................................133
Figure 9.4 S
pectra of adsorbed species persisting on MIL-100 after
outgassing at 423 K, subtracted from spectra at 373 K.....................137
Figure 9.5 O
ptimized structure (B3LYP/LANL2DZ) of complex formed
by cluster Fe3O(OH)L6 with indole. Large gray atoms, Fe;
black atoms, C; small white atoms, H; red atoms, O; blue
atom, N (color figure online)...........................................................139
Figure 10.1 R
epresentative aromatic sulfur compounds. (a) Thiophene;
(b) 3-methylthiophene (3-MT); (c) benzothiophene (BT); (d)
dibenzothiophene (DBT).................................................................146
List of Figures xix
Figure 10.2 M
etal-organic framework with –SO3Ag for adsorptive
desulfurization.................................................................................154
Figure 10.3 S
ite-selective functionalization of MIL-101 with unsaturated
metal sites: (a) perspective view of the mesoporous cage
of MIL-101 with hexagonal windows; (b,c) evolution of
coordinatively unsaturated sites from chromium trimers
in mesoporous cages of MIL-101 after vacuum treatment
at 423 K for 12 h; (d) surface functionalization of the
dehydrated MIL-101 through selective grafting of amine
molecules (i.e., ethylenediamine) onto coordinatively
unsaturated sites; (e) selective encapsulation of noble metals in
the amine-grafted MIL-101 via a three-step process (see text).
Chromium atoms/octahedra, yellow; carbon atoms, pale gray;
oxygen atoms, red............................................................................159
Figure 11.2 C
hlorinated aromatic compounds as in Kim et al. (2013): (a)
chlorobenzene, (b) 2-chlorotoluene, (c) 1,3-dichlorobenzene,
and (d) 2-chloroanisole....................................................................170
Figure 11.3 T
he APIs used in the study. (Centrone, A. et al., Small, 7(16),
2356, 2011.).....................................................................................170
Figure 13.1 N
itrogen sorption isotherms and their corresponding
BET surface areas for non/stirring experiments of large-
scale preparations of MIL-101(Cr); filled symbols are for
adsorption and empty symbols for desorption. The synthesis
and treatment of both the products followed the general
procedure. The BET surface areas were calculated in the
pressure range 0.05 < p/p0 < 0.2 from N2 sorption isotherms at
77 K with an estimated standard deviation of ±50 m2/g................201
List of Tables
Table 2.1 P
ostsynthetic Modifications of MIL-101(Cr) Based on Chemical
Reactions of Adsorption..........................................................................6
Table 2.2 P
SMs of MIL-101 via Covalent Bonding to the –NH2 Group in
the Linker.................................................................................................8
Table 2.3 Postsynthetic Modifications of MIL-100 via Adsorption......................15
Table 3.1 S
tudies of Activation of MIL-100 and Similar MOFs for
Adsorption and Catalysis Applications.................................................29
Table 4.1 Stability of Pure MIL-101(Cr) in Water................................................38
Table 4.2 Stability of Chemically Modified MIL-101(Cr) in Water.....................40
Table 4.3 Stability of MIL-101 Other Than MIL-101(Cr) in Water......................44
Table 4.4 Stability of Pure MIL-100(Fe) in Water................................................48
Table 4.5 Stability of Pure MIL-100(Cr) in Water................................................49
Table 4.6 Stability of Pure MIL-100(Al) in Water................................................51
Table 4.7 S
tability of Mesoporous MOFs Other Than MIL-101 and
MIL-100 in Water, 2012–2014..............................................................54
Table 4.8 S
tability of Mesoporous MOFs Other Than MIL-101
and MIL-100 in Water, Papers Since 2014............................................58
Table 5.1 Adsorption of Cationic Organic Dyes on MIL-101 from Water...........69
Table 5.2 Adsorption of Cationic Organic Dyes on MIL-100 from Water...........72
Table 5.3 Adsorption of Anionic Dyes on MIL-101 in Water, 2010–2012...........76
Table 5.4 Adsorption of Anionic Dyes on MIL-101 in Water Since 2014............77
Table 5.5 A
dsorption of Anionic Dyes on MIL-100 and Other
Mesoporous MOFs in Water, 2013........................................................80
Table 5.6 Adsorption of Anionic Dyes on MIL-100 in Water Since 2014............81
Table 6.1 A
dsorption of Small-Molecule Medicinal Drugs on Pure and
Modified MIL-101 in Aqueous Solutions..............................................88
Table 6.2 A
dsorption of Small-Molecule Medicinal Drugs on Pure
MIL-100 in Aqueous Solutions.............................................................90
Table 6.3 A
dsorption of Biocompounds on Mesoporous MOFs with BDC
and BTC Linkers...................................................................................94
xxiii